Metal hydrocarbyl orthophosphate gasoline additive



United States Patent 18 Claims ABSTRACT OF THE DISCLOSURE A metal hydrocarbyl orthophosphate gasoline additive composition is disclosed, wherein the additive is in the amount of between 0.001 and about 5.0 times the theoretical amount (theories) to react stoichiometrically with the lead in the gasoline combustion product. A preferred metal hydrocarbyl orthophosphate additive is represented by the general formula:

wherein M represents manganese, thorium, and metals of Groups LB, II-A, VI-B and VIII of the Periodic Table, n is a number equal to the valence of the metal M, and R and R each represent hydrocarbyl radicals having from 2 to 30 carbon atoms and soluble to the required extent in gasoline; preferably at least one of the R and R radicals represents a branched chain hydrocarbyl radical.

This invention relates to novel and improved gasolene compositions containing certain metallic orthophosphate compounds.

This application is, in part, a continuation of my copending application, Ser. No. 413,631, filed Nov. 24, 1964, which in turn is a continuation-in-part of my copending application Ser. No. 127,858, filed July 31, 1961, now abandoned.

The use of lead compounds to increase the octane rating of gasolene is extremely common. Unfortunately, the addition of lead, while substantially increasing the octane ratings of gasolenes to which it is added, at the same time has several drawbacks. Of these drawbacks, the most serious is probably the tendency of the lead to increase undesirable surface ignition in the combustion chambers of the internal combustion engines in which the leaded gasolene is used. It has been the practice previously to utilize various phosphorus compounds in an attempt to reduce or prevent such surface ignition, but the use of such compounds has generally led to additional ditliculties, such as lead deposits on cylinder heads and valves.

It is, therefore, an object of the invention to provide an improved gasolene composition.

It is a further object of the invention to provide an improved gasolene composition especially adapted to resist surface ignition.

The improved gasolene compositions provided by the invention comprise as additive compounds metallic orthophosphates represented by the general formula:

wherein M represents a metal selected from the group consisting of manganese and thorium and Groups I-B, II-A, VI-B and VIII of the Periodic Table, X is halogen, n and 3,445,206 Patented May 20, 1969 a are numbers so selected that 2: equals the valence of the metal M and 0 equals Zero except when the valence of the metal M equals 5, then a equals 2 and n equals 3, and R and R each represent a hydrocarbon radical having from 2 to about 30 carbon atoms. Preferred metallic orthophosphates for the purpose of this invention are those represented by the general formula:

wherein M, R and R are as defined above and n is an integer of from 2 to 4 and is equal to the valence of the metal M. In such compounds the valence of the metal M usually depends upon the starting material used. Preparation of these compounds is discussed in greater detail below.

R and R may represent identical or different hydrocarbon radicals. While any hydrocarbon radical having between 2 and about 30 carbon atoms and soluble to the required extent in gasolene may be used, at least one of R and R preferably represents a branched-chain acyclic hydrocarbon radical. Such radicals are generally more soluble in gasolene than other hydrocarbon radicals, thereby facilitating the use of the novel compounds of the present invention as gasolene additives. Since chains of more than about 30 carbon atoms are generally difi'icult or impossible to dissolve in gasolene compositions, it is preferred that the hydrocarbon radicals of the orthophosphates utilized in the present invention each have between about 2 and about 30 carbon atoms. It is particularly preferred that the hydrocarbon radicals represented by R and R be acyclic aliphatic hydrocarbon radicals containing from about 6 to about 22 carbon atoms, particularly C to C branched-chain aliphatic hydrocarbon radicals.

Typical R and R groups would include, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, heXyl, isohexyl, 2,2,4-trimethylpentyl, S-methylpentyl, 2,2- dimethylbutyl, 2,3-dimethylbutyl, heptyl, isoheptyl, 3- methylhexyl, 3,3-dimethylpentyl, octyl, 2,3-dimethylhexyl, 2,4-dimethylhexyl, 2-ethylhexyl, 2-ethylbutyl nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonyldecyl, eicosyl, hencosyl, docosyl, tricosyl, tetracosyl, pentacosyl, hexacosyl, heptacosyl, octacosyl, nonacosyl, triacontyl, phenyl, naphthyl, benzyl, o-cresyl, p-cresyl, m-cresyl, dodecylphenyl, octylphenyl, ethylphenyl, diphenyl, B-phenylethyl, omegaphenylhexyl, cyclohexyl, cyclobutyl, cyclodecyl, cyclopentyl, butenyl, octenyl, 2,3-dimethylpentenyl, Z-ethyl hexenyl, linoleyl, oleyl, etc.

Compounds of the present invention having branchedchain alkyl hydrocarbon radicals include, for instance, the following:

nickel di[bis (2-methylpropenyl) orthophosphate] manganese di[bis (S-butyloctacosyl) orthophosphate] copper di[bis (S-pentylhexadecyl) orthophosphate] beryllium di[bis (Z-ethyl-S-butyltridecyl) orthophosphate] silver [bis (2,4-diethyloctyl) orthophosphate] chromium tri[bis (Z-methyloctenyl) orthophosphate] iron tri[bis (i-propyl) orthophosphate] nickel di[bis (2-ethylhexyl) orthophosphate] molybdenum HI tri[i-propyl, propyl orthophosphate] magnesium di[i-propyl, 2-propyldecyl orthophosphate] nickel di[bis (isodecyl) orthophosphate] ruthenium tri[Z-ethylhexyl, butenyl orthophosphate] osmiumII[ (2-ethylhexyl, octyl), (i-puropyl, butyl) orthophosphate] nickel di[isodecyl, 2-cthylhexyl orthophosphate] tungsten hexa[2-ethylhexyl, i-butyl orthophosphate] 3 dichloromolybdenum tri[bis (Z-ethylhexyl) orthophosphate] chromium tri[bis (2,3-dimethylpentenyl) orthophosphate] magnesium di[bis (Z-ethylhexyl) orthophosphate] Compounds of the present invention having alkylaryl hydrocarbyl radicals include, for instance, the following:

thorium tetra[bis (methylphenyl) orthophosphate] tungsten hexa[bis (octylphenyl) orthophosphate] nickel di[bis (methylphenyl) orthophosphate] calcium di[bis (pentylphenyl) orthophosphate] gold tri[octylphenyl, pentylphenyl orthophosphate] strontium di[bis (methylphenyl) orthophosphate] nickel di[bis (hexylphenyl) orthophophosphate] cobalt tri[bis (methylnaphthyl) orthophosphate] rhodium II[(pentylnaphthyl, propyl) di (methylphenyl) orthophosphate] dichloromolybdenum tri[bis (ethylphenyl) orthophosphate] Compounds of the present invention having both alkyl and alkylaryl hydrocarbyl radicals include, for instance, the following:

barium di[2-ethylhexyl, methylphenyl orthophosphate] iridium II[(butyl, ethylhexyl), (methylphenyl, propyl) orthophosphate] Compounds of the present invention having aryl hydrocarbyl radicals include, for instance:

radium di[bis (phenyl) orthophosphate] palladium tri[phenyl, naphthyl orthophosphate] nickel II di[naphthyl, 2-ethylhexyl orthophosphate] Compounds of the present invention having arylalkyl hydrocarbyl radicals include, for instance:

nickel di[bis (phenylmethyl) orthophosphate] platinum II[ (naphthylethyl, butyl), (Z-ethylhexyl, phenylhexyl) orthophosphate] nickel di[i-butyl, naphthylmethyl orthophosphate] Compounds of the present invention having alicyclic hydrocarbyl radicals include, for instance:

nickel di[cyclobutyl, Z-ethylhexyl orthophosphate] cobalt tri[bis (cyclohexyl orthophosphate] manganese di[bis (cyclohexyl orthophosphate] calcium di[bis (cyclopentyl orthophosphate] Compounds of the present invention having straight chain hydrocarbyl radicals include, for instance, the following:

cobalt tri[bis (octyl) orthophosphate] magnesium di[bis (octenyl) orthophosphate] nickel di[bis (ethyl) orthophosphate] calium II[di (butyl), di(pentyl) orthophosphate] nickel di[2-ethylhexyl, butenyl orthophosphate] nickel di[(butyl, isodecyl) orthophosphate] copper di[bis (decyl) orthophosphate] The novel compounds described above are especially useful as gasolene additives in forming novel gasolene compositions adapted to resist surface ignition. In addition to resisting surface ignition, these additives generally inhibit rust and carburetor icing. In accordance with a preferred embodiment of the present invention a gasolene composition is provided which comprises a major proportion of a leaded hydrocarbon base fuel boiling in the gasolene range and containing between about 0.001 and about 5.0 theories of a metallic hydrocarbyl orthophosphate of the type described above. The leaded hydrocarbon base fuel comprises at least 50 volume percent and preferably at least 75 volume percent of the gasolene composition.

By the term leaded gasolene, leaded hydrocarbon base fuel boiling in the gasolene boiling range and similar terms is meant a petroleum fraction boiling in the gasolene range (e.g., between about 50 and about 450 F.) to which has been added a small amount, such as between about 0.1 and about 6.0 cc. per gallon, of -a metallo-organic antiknock compound such as tetraethyl lead (TEL), tetramethyl lead (TML), tetraisopropyl lead, etc. Lead is frequently present in gasolene compositions of the present invention in the form of TEL, TML or mixtures of the same which may be present in suitable amounts such as between about 0.1 and about 6.0 cc. per gallon of gasolene composition, more usually between 0.5 and about 4.0 cc. per gallon.

The novel metallic orthophosphates described above for use in leaded gasolene compositions in accordance with the present invention are present in suitable amounts such as between about 0.001 and about 5.0 theories, preferably between about 0.02 and about 2.0 theories. The term theory" in this context is intended to designate the amount of metal hydrocarbyl orthophosphate additive that would be needed in a gasolene in order that the metal and phosphorus atoms in the metal hydrocarbyl orthophosphate would be able to react stoichiometrically with all the lead in the lead antiknock compound present in a gasolene to form the appropriate lead compound upon combustion in an engine. The theory concept may be based on the metal only, on the phosphorus only, or on both elements in the metal hydrocarbyl orthophosphate. Thus, for example, the additive dichloromolybdenum tri[bis(2-ethylhexyl) orthophosphate] could react with TEL and T ML to produce lead orthophosphate and lead molybdate. In this example the theories of additive employed would be based on the phosphorus required to form lead orthophosphate and on the metal molybdenum to produce lead molybdate. If the metal in the metal hydrocarbyl orthophosphate additive does not combine with the lead in the gasolene to form a compound upon combustion in an engine, then the theory concept is based on the phosphorus in the additive. To illustrate, nickel di[bis(isodecyl) orthophosphate] in a gasolene with TEL "forms only lead orthophosphate upon combustion, as no compounds of lead with nickel are known to exist.

In addition to the above-described compounds, gasolene compositions contemplated by the present invention may include one or more other ingredients such as lead scavengers, gum inhibitors, lubricants, rust inhibitors, metal deactivators or other special purpose additives.

Lubricants suitable for use in the above-described gasolene compositions may include, for instance, light hydrocarbon lubricating oils having viscosities at F. of

between about 50 and about 200 Saybolt Universalseconds (SUS) and viscosity indexes (VI) of between about 30 and about with oil having a viscosity of about 100 SUS being preferred. Such oils may be present in suitable amounts such as between about 0.1 and about 1.0 volume ercent of the gasolene composition.

When using lead compounds such as TEL, it is frequently found desirable to include with the lead a suitable lead scavenger for reducing the deposit of lead compounds Within the combustion chamber. Such lead scavengers include, for example, halohydrocarbon compositions such as ethylene dibromide and ethylene dichloride.

Gum inhibitors suitable for use in the above-described gasolene compositions include conventional gum inhibitors such as 2,6-di-tert-butyl-p-cresol. Such gum inhibitors may be present in suitable amounts such as between about 0.001 and about 0.006 volume'percent of the gasolene composition. Likewise, a suitable metal deactivator is for example N,N'-disalicylidene-1,2-diaminopropane.

Gasolene compositions of the present invention may be illustrated by the following examples. It should be understood that any of the other novel additive compounds contemplated by the invention, such as those described above, may be used in such gasolene compositions in place of or in addition to the additives specified below.

Example 1 A gasolene composition having excellent surface ignition characteristics may be prepared by adding the following ingredients to a suitable base gasolene:

TEL cc. per gallon-.. 2.2 Dichloromolybdenum tri[bis(2 ethylhexyl) orthophosphate] theories 0.05

The base gasolene used in blending this and other gasolene compositions of the invention may be a gasolene having the following characteristics:

Distillation:

IBP 101 F.-

10% evaporation F 130 20% F 149 30% F 168 50% F 210 70% F 260 90% F 328 End point F 409 Recovery percent 98.5 Residue do 1 Gravity API 58.2

Example 2 Another suitable gasolene composition is prepared by adding the following ingredients to a suitable base gasolene:

TEL cc. per gallon" 0.5 Cobalt [(propyl, cyclopentyl) di(2 ethylhexyl) orthophosphate] theories 0.25

Example 3 Another suitable gasolene composition is prepared by adding the following ingredients to a suitable base gasolene:

TEL 4.0 cc. per gallon. Manganese di[(2-ethylhexyl, octyl) orthophosphate] 0.5 theories. Lubricating oil 1.0 volume percent (100 SUS, 95 VI).

Example 4 Another suitable gasolene composition is prepared by adding the following ingredients to a suitable base gasolene:

TEL cc. per gallon 6.0 Nickel di[bis(2-ethylhexyl) orthophosphate] theories 5.0

Example 5 TEL cc. per gallon 0.1 Magnesium di[bis(2-ethylhexyl) orthophosphate] theories 0005 Example 6 Another suitable gasolene composition is prepared by adding the following ingredients to a suitable base gasolene:

TEL 2.2 cc. per gallon. Chromium tri [bis(triacontylphenyl) orthophosphate] 0.1 theories. Lubricating oil 0.25 volume percent (100 SUS, 95 VI). Example 7 Another suitable gasolene composition is prepared by adding the following ingredients to a suitable base gasolene:

TML cc. per gallon 2.5

Chromium di[bis(o-cresyl) orthophosphate] ..theories 0.15

Example 8 Another suitable gasolene composition is prepared by adding the following ingredients to a suitable base gasolene:

Another suitable gasolene composition is prepared by adding the following ingredients to a suitable base gasolene:

TML cc. per gallon 4.0 Iron tri[2-ethylhexyl, a-naphthyl orthophosphate] theories 3.5

Example 10 Another suitable gasolene composition is prepared by adding the following ingredients to a suitable base fuel:

TEL cc. per gallon..- 2.33 Osmium tetra[bis(0ctyl) orthophosphate] theories 2.0

Example 11 Another suitable gasolene composition is prepared by adding the following ingredients to a suitable base fuel:

TEL cc. per gallon 1.8 Thorium tetra[bis(cyclohexyl) orthophosphate] theories 1.8

Example 12 Another suitable gasolene composition is prepared by adding the following ingredients to a suitable base fuel:

TEL cc. per gallon..- 1.2 Manganese di[bis(linoleyl) orthophosphate] tl1e0ries 1.5

The metallic orthophosphate compounds utilized additives in accordance with the present invention may be prepared in any suitable manner. According to one method of preparation, a suitable organic hydrogen phosphate or a mixture of such phosphates is placed in a reaction flask together with about half its volume of a suitable solvent such as dry toluene. The reaction flask is preferably equipped with a mechanical stirrer, thermometer, gas inlet tube, reflux condenser and a pressure equalizing funnel with its long steam dipping into the solution. The temperature in the reaction flask is raised to between about 110 and about 130 C. while stirring vigorously and a suitable salt such as a chloride of the desired metal with an equal volume of the solvent is added in spurts by means of the pressure equalizing delivery funnel. When a chloride is used, hydrogen chloride is evolved copiously by the reaction. Stirring and heating under reflux to 130 C. is continued until evolution of hydrogen chloride stops. Removal of by-product hydrogen chloride is promoted by flushing the reaction flask with dry nitrogen by means of the gas inlet tube. The solvent is removed by distillation at reduced pressure such as 10 to millimeters, the final temperature being about 130 C. The yield of product is usually between about and about of theory based on hydrogen phosphate.

Example 13 Nickel di[bis(2-ethy1hexyl) orthophosphate] was prepared from the following ingredients:

32.6 gm. (0.137 mole) nickel chloride hexahydrate 80.6 gm. (0.25 mole) di(2-ethylhexyl) hydrogen phosphate gm. sodium hydroxide in 100 ml. water The acid phosphate was weighed into a 3-neck round bottom flask equipped with mechanical stirrer, thermometer, and condenser. About 100 ml. of Water was added to the flask and the mixture was stirred while the sodium hydroxide solution was added slowly. The temperature in the flask rose from 26 to 46 F. About 200 ml. of

7 toluene was added and the temperature increased by external heating to 80 C. At this time the nickel chloride hexahydrate in 50 ml. of H was added. The reaction temperature was raised to 87 C. and maintained at this level with vigorous stirring for 16 hours. After this time The base gasolene of run 4 contained 2.03 cc. per gallon TEL. The single cylinder engine deposit tests were run in CPR engines having L head assemblies and compression ratios of 7 to 1. Each test consisted of alternating periods of operation under idling conditions for 50 seconds folthe contents were transferred to a separatory funnel and lowed b operation under full lo d conditions for 150 the aqueous phase drawn off and discarded. The organic seconds. These cycles were continued for a total test time layer was washed with water, dried over anhydrous of 40 hours for each test. During these tests the engine air Na SO filtered to remove the hydrated salt and finally intake temperature was maintained at 115 F. while the subjected to distillation to remove solvent. oil temperature was maintained at 160 F. and the coolant The product was a brown, viscous material. 10 temperature at 150 F. During the idling portions of the Example 14 tests the engines were operated with an air to fuel ratio of 12 to 1 at 600 rpm. while during the full load portions In Order to P p dichlofomolybdenum U Q' of the tests the engines were operated with air to fuel y y p p l, 212 gr 3111s H1016) of 15 ratios of 13 to 1 and at 900 rpm. During the test, the numcommel'cial Q- Y Y yd Phosphate in 150 ber of wild pings (indicating preignition) was counted by 0f toluene and 55 grams l molybdenum an Erwin Instrument Co. Wild Ping Counter. At the end pentachloride in 200 ml. of toluene were caused to react. f the test the average of the Wild pings per was deter- When evolution of y-p hydrogen Chloride Stopped, mined by plotting the total wild pings versus time and toluene Was pp from the Product, Which was then taking the slope of the curve. This measurement served as Washed With Water and taken p in -p After a reliable indication of the surface ignition characteristics ing over anhydrous sodium sulfate, the pentane solution f h f l b i t t d, was filtered and the filtrate subjected t0 distillation to 1'6- The results of the single cylinder engine deposit test move P The liquid residue was heated to are given in Table I below. Each run involved a test of a at 20 mm- PI6SSI1fe- All Olive green liquid Product Weigh base gasolene and a test of the same base gasolene coniflg 203 grams resulted- Its density Was 1-109 at and taining the indicated metallic orthophosphate additive. the molybdenum content Was Percent While the base gasolenes used were generally similar, they Add metallic Orthophosphate additives were P had been stored for varying lengths of time before testing, pared according to the Procedures described above 0111 thus affecting their performance in the tests. The test re- Su Starting materials as follows: sults reported below thus prove valid comparisons within Amount Amount each run between the performance of a'base gasolene and Starting materials (grams) Product (grams) the performance of the same gasolene containing the indi- Cobaltous acetate 62 Cobalt dflbisemhyh 158 cated additive but do not provide valid comparisons betetrahydrate, orthophostween the base gasolenes used in the various runs.

P L D%i(36ggl111y1l)lfi% %1galey- 161 TAB E I. RESULTS %B E%%I OYLINDER ENGINE Manganous chloride 22 Manganese d1 [bis(2- 60 tetrahydrate. ethylhexyl) ortho- Average wild pings phosphate]. per hour of base Di(2-ethy1hexy1) hy- 64. 5 gasoline droge plmsphate 40 Run Orthophosphate additive Theories Without With Other compounds of the present invention may be pre- (additive additive additive pared from suitable starting materials. For instance, the 1 Cobalt di[bis(2-ethy1- 0.2 21 2 following compounds may be prepared from the indicated 2 gggg g giggzgg ggi 0. 2 31 1 starting materials with the use of suitable solvents such hexyDptthophosphate]. as toluene, heptane, etc. 3 if ig ggg gfffg g 19 1 4 Diehloromolybdeniim m 0. 05 586 15 Amount [bis(2-ethylhexyl) ortho- Startingmaterials (grams) Product phosphate].

Magnesium chloride 56 ggg s gg g lgz t -gg Table I shows clearly that the addition of metallic ortho- Di(2 th 1h hydrogen 161 y p p phosphates of the present invention to the base gasolenes ggg 'ggfi n5 Chmmiummmuflacm resulted 1H q g composltwqs P s e y much ylphenyl) orthophosphatal proved surface ignition characteristics as evidenced by the Trialggntil ggghenyl-hydrogen 178.2 extremely small number of wild pings compared with the Ciironiious chloride 13.4 Chrg i niu n dl wisgo-cresyl) gfi li ig g g g d b d b or op os ia e. 1e e invention as een escri e a ove with reggi hydwgen P1105 55 spect to certain preferred embodiments thereof, it will be Tungsten tetrachloride 35.8 Tunglsten tletrabisgtlz-paphunderstood by those skilled in the art that various changes Dil(1a n?hthy1)hydmgen 14o thy) osp alrlid modifications mag 26 made without departing from p osp ate. t e spirit an scope o t e invention and it is intended to mmde gg ggggggfggggeg g cover all such changes and modifications in the appended 2-Ei1thgrl2ergl, gtslsmggglyh 108.9 60 claims. nuiiiouiirm ietrs ohloridonm 13.3 Ruthenium tetra[bis(oct,yl- Therefore I clam Di(octylphenyl) hyd m5 p enyl) ortho hosphate]. A gasolene composition consisting essentially of a phosphate ma or proportion of a leaded hydrocarbon base fuel boilmg in the gasolene range and containing between about In order to evaluate the characteristics of gasolene com- -001 nd about 5.0 theories of an additive having the positions of the present invention, a number of gasolene formula: compositions were prepared containing metallic ortho- 0 0R phosphate additives of the present invention as indicated M {L in Table I below. These gasolene compositions Were subjected to single cylinder engine deposit tests as OR descnbed l w- T e b gasolenes edjn formulating wherein M is a metal selected from the group consisting the gasolene compositions tested were similar to the base of manganese and thorium and the metals of Groups LB, gasolene 0f Examplfi The base gasolenes of s II-A, VIB and VIII of the Periodic Table n equals the 1 through 3 Contained P ga EIJ and 0.25 valence of metal M, and R and R each represent a hyo p n 100 eu (95 llght u l g o drocarbon radical having from2to about30 carbon atoms.

2. A gasolene composition as in claim 1 wherein said metal is manganese.

3. Gasolene composition as in claim 1 wherein at least one of R and R' is a branched-chain hydrocarbon radical.

4. Gasolene composition as in claim 3 wherein said metal is nickel and n is 2.

5. Gasolene composition as in claim 1 wherein R and R are acyclic alpihatic hydrocarbon radicals containing from about 6 to about 22 carbon atoms.

6. Gasolene composition as in claim 5 wherein both R and R' are branched-chain hydrocarbon radicals.

7. Gasolene compositions as in claim 6 wherein said metal is nickel and n is 2.

8. Gasolene composition as in claim 1 which contains between about 0.02 and about 2.0 theories of said additive.

9. Gasolene composition as in claim 1 wherein said leaded hydrocarbon base fuel is a petroleum fraction boiling between about 50 C. and about 450 C. to which has been added between about 0.1 and about 6.0 cc. per gallon of tetraethyl lead.

10. Gasolene composition as in claim 9 wherein the amount of tetraethyl lead is from about 0.5 to about 4.0 cc. per gallon.

11. Gasolene composition as in claim 1 wherein said additive is cobalt di[bis(2-ethylhexyl) orthophosphate] 12. Gasolene composition as in claim 1 wherein said additive is manganese di[bis(2-ethylhexyl) orthophosphate].

13. Gasolene composition as in claim 1 wherein said additive is nickel di[bis(2-ethylhexyl) orthophosphate].

14. Gasoline composition as in claim 1 wherein said additive is nickel di[bis(isodecyl) orthophosphate].

15. Gasoline composition as in claim 1 wherein said metal is nickel, n is 2, and R and R are alkylaryl groups.

16. Gasoline composition as in claim 1 wherein said additive is nickel di[bis(rnethyl phenyl) orthophosphate].

17. Gasoline composition of claim 1 wherein said R and R groups are arylalkyl groups.

18. Gasoline composition of claim 10 wherein said additive is in the amount of between about 0.02 and 2.0 theories, said additive being nickel di[bis(isodecyl) orthophosphate].

References Cited UNITED STATES PATENTS 2,560,542 7/1951 Bartleson et al 4468 3,055,748 9/ 1962 Hartle 260-437 2,055,925 9/1962 Hartle 260-437 3,065,065 11/1962 Sutton et a1 4468 DANIEL E. WYMAN, Primary Examiner.

Y. H. SMITH, Assistant Examiner.

US. Cl. X.R. 44-68. 76 

